US4490494A - Dyeable polymer alloy fibers containing a polymeric dye-receptor and a metal salt of a carboxylic acid - Google Patents

Dyeable polymer alloy fibers containing a polymeric dye-receptor and a metal salt of a carboxylic acid Download PDF

Info

Publication number
US4490494A
US4490494A US06/562,029 US56202983A US4490494A US 4490494 A US4490494 A US 4490494A US 56202983 A US56202983 A US 56202983A US 4490494 A US4490494 A US 4490494A
Authority
US
United States
Prior art keywords
composition
weight percent
matter
accordance
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/562,029
Inventor
Robin D. Shropshire
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Phillips Petroleum Co
Original Assignee
Phillips Petroleum Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Priority to US06/562,029 priority Critical patent/US4490494A/en
Application granted granted Critical
Publication of US4490494A publication Critical patent/US4490494A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/12Applications used for fibers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869Acids or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • This invention relates to dyeable polymer alloy fibers.
  • this invention relates to dyeable olefinic polymers and, in particular, to polypropylene.
  • these patents product a dyeable composition by blending with the olefin polymer, dye receptors such as those delineated in the above patents.
  • These include polyamides which are polycondensates of cyclic amides, and polyamides which are polycondensates of aliphatic diamines with dicarboxylic acids, polyurethanes, polyureas, polyesters which are polycondensates of alkylene glycols with dicarboxylic acids, reaction products of polyalkyleneimines containing 2 to 20 carbon atoms with a substance selected from the group consisting of chlorinated paraffin waxes, diisocyanates, lower aliphatic acid anhydrides, hydrohalogen acids and monobasic fatty acid chlorides.
  • Such dye receptors include mixtures of a polyalkyleneimine in which the alkylene group contains from 2 to 20 carbon atoms with the reaction product of epoxy resin obtained by reacting epichlorohydrin and 4,4'-dioxyphenyldimethyl-methane and monoethanolamine.
  • Such dye receptors also include thermoplastic polymers of vinyl-substituted mono- and polycyclic pyridine bases, thermoplastic polyamides, including condensation homopolymers and copolymers having pendent groups, containing or consisting of amide groups, and amine polymers, including condensation homopolymers and copolymers, in which the amine group is an integral part of the polymer chain, and addition homopolymers and copolymers having pendent groups which include or consist of amine groups and other basic nitrogen polymers such as polyurethanes, polyureas, poly(vinyl carbazoles) and aniline-formaldehyde resins.
  • this invention is applicable to any of the olefin polymers but is particularly applicable to polypropylene.
  • any dye receptor which when blended with an alpha-monoolefin improves the dye receptivity of the alpha-monoolefin, can be used in this invention.
  • the olefin polymer will have blended with it any of the aforementioned polymers such as polyamides, polyurethanes and the like as recited in U.S. Pat. Nos. 3,107,228, 3,312,755 and 3,361,843, which substances are referred to hereinafter generally as "dye receptors".
  • the blend of the olefin polymer and the dye receptor will be comprised of up to about 50 weight percent of the dye receptor, an amount in the range of from 1 to about 40 weight percent being preferably employed, the olefin polymer and the dye receptor containing stabilizers, antioxidants and other constituents in conventional amounts.
  • Preferred dye receptors are polyamides such as nylon-6,6, nylon-6,10, nylon-6, du Pont's Zytel 63, a polymer consisting of nylon-6,6, nylon-6,10 and nylon-6 in a ratio of about 40:40:20, and du Pont's Acid Dye Additive PB 7007, a copolymer of ethylene and an amino alkyl acrylate, specifically a 70/30 ethylene/N,N-dimethylaminoethyl methacrylate copolymer.
  • Any metal salt of carboxylic acid metal salt which contains 4 to 18 carbon atoms can be used.
  • Suitable carboxylic acids are benzoic acid, p-t-butylbenzoic acid, phenylacetic acid, mellitic acid, 1,8-naphthalic acid, o-phthalic acid, 1,2-cyclohexanedicarboxylic acid, adipic acid, succinic acid, and camphoric acid, stearic acid, and the like.
  • Preferred metals are those of Group IA and Group IIIA of the Periodic Table. It is preferred that the metal salt be finely divided for best results. For example, it is desirable that the salt can pass through a 100 mesh screen or finer, i.e., 325 mesh screen.
  • suitable metal salts include sodium benzoate, potassium benzoate, lithium benzoate, sodium stearate, potassium adipate, lithium phenylacetate, aluminum hydroxy p-t-butylbenzoate, and the like.
  • the carboxylic acid metal salt will be employed in an amount up to about 3 weight percent based upon the polyolefin content of the polymeric blend although amounts within the range of from about 0.25 to 1 weight percent are preferred.
  • the blend of the olefin polymer, the dye receptor and the carboxylic acid metal salt can be prepared in any manner resulting in a homogeneous mixture.
  • the olefin polymer and dye receptor are melt blended and the salt is mixed into the blend.
  • Preferred blends contain from about 89.5 to 97 weight percent polypropylene, about 3 to about 10 weight percent of Dye Additive PB 7007, and about 0.25 to 1 weight percent sodium benzoate.
  • Olefin polymers and especially polypropylene, require protection against thermal and oxidative degradation and hindered phenolic antioxidants such as Irganox 858, 1010, 1076, and 1093 are excellent for this purpose. These materials are manufactured by the Geigy Chemical Corporation, as disclosed in U.S. Pat. No.
  • 3,285,855 are, respectively, 2,4-bis(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octylthio)-1,3,5-triazine, tetrakis [methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, octadecyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)]propionate and di-n-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate.
  • These antioxidants are particularly effective because of their low volatility and long term beneficial effects.
  • antioxidants such as BHT(2,6-di-t-butyl-4-methylphenol), Ethyl 330 (Ethyl Corp.), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene can also be used.
  • These primary antioxidants are generally used in amounts ranging from about 0.005 to about 1 weight percent, based on total composition, and more preferably from about 0.02 to about 0.5 weight percent.
  • a second antioxidant to supplement or augment the effectiveness of the primary one is generally used in polypropylene formulations.
  • a particularly effective class of such compounds are the diesters of beta,beta'-dithiopropionic acid. Especially preferred for this purpose are dilaurylthiodipropionate (DLTDP) and distearylthiodipropionate (DSTDP). These compounds are used in amounts ranging from about 0.02 to about 3 weight percent, based on total composition, and more preferably from 0.05 to about 1.5 weight percent.
  • a processing aid is generally used in preparing fibers from polypropylene compositions.
  • This material is an alkaline earth metal stearate, preferably calcium stearate. These compounds are used in amounts ranging from about0.005 to about 2 weight percent, based on total composition, and more preferably from about 0.02 to about 0.5 weight percent.
  • a UV stabilizer is required to impart light stability and dye lightfastness to the compositions.
  • the hydroxybenzotriazoles are effective when used for this purpose. These compounds are represented by the following generic formula: ##STR1## in which R 1 and R 2 can be hydrogen or an alkyl group containing from 1 to 12 carbon atoms with at least one R 1 or R 2 being an alkyl group and R 3 is a halogen such as chlorine or hydrogen. Particularly preferred is the combination wherein R 1 and R 2 are C 5 and R 3 is hydrogen.
  • This compound is 2(2'-hydroxy-3',5'-di-t-amylphenyl)benzotrizole (Tinuvin 328).
  • the UV stabilizer is used in amounts ranging from about 0.1 to about 2 weight percent, based on total composition, and more preferably from about 0.25 to 1.5 weight percent.
  • composition consists of:
  • any of the usually employed dye receptors are blended with an olefin polymer, there is formed an alloy which possesses a dyeability greater than that possessed by the olefin polymer in respect to disperse and acid dyes but substantially no greater than that possessed by the olefin polymer in respect to cationic dyes.
  • K/S color determinations were made, these employing a colorant-mixture computer devised by Davidson and Hemmendinger, an analogy instrument employing the Kubelka-Munk K/S function. The results are presented below with the higher K/S color values indicating the greater dyeability.
  • Blends of polypropylene and Rhodiaceta DD Nylon 66, a polyamide dye receptor, were prepared by melt blending, the blends differing in respect to their polyamide content. To individual portions of these blends sodium benzoate was added.
  • Blends of polypropylene and a polymer comprising a 70/30 ethylene/N,N-dimethylaminoethyl methacrylate copolymer as the dye receptor were prepared, the blends containing 7 percent of the dye receptor.
  • the blends of these polymers were printed, as fibers, with various dyes using 1 percent dye in a dye paste.
  • compositions of this invention are particularly employable as melt-spun fibers because of the depth of dye penetration effected by the components of the composition. As such they are particularly suitable for fabrics subjected to frequent dry cleaning because of the dry cleaning fastness of these fibers.
  • heat stabilization of the fibers of the examples was accomplished by steaming in an autoclave.
  • the heat stabilization can be by heat setting such that the dyeable fiber will be maintained at a higher temperature for a much longer period than is usually the case in fiber line drawing.
  • Fiber 12 was a polypropylene fiber containing the aforementioned 7% by weight of du Pont's Acid Dye Additive PB 7007 and 1% by weight of sodium benzoate.
  • Fiber 6 was the same polypropylene fiber containing 7% by weight of du Pont's Acid Dye Additive PB 7007.
  • the fibers were exposed for 20 standard fading hours to a carbon arc and were then dyed, in pairs, in competitive dyeing with an unexposed sample of the same composition, the resulting dye uptake being as follows:
  • the fibers, as described, were heated in an autoclave at 212° F. for an identical period of time.
  • the fibers were then dyed in competitive dyeing, in pairs, with the following results:
  • the fibers were heated in an autoclave at 212° F. to heat-stabilize them and then exposed for 20 standard fading hours to a carbon arc and thereafter competitively dyed. Results were as follows:
  • compositions in the preceding examples all contained additives not specifically named.
  • the compositions contain stabilizing amounts of dilaurylthiodipropionate (0.25 weight percent based on the polypropylene) and 2,4-bis(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octylthio)-1,3,5-triazine (0.08 weight percent based on the polypropylene) as antioxidants and 0.05 weight percent calcium stearate (based on the polypropylene) as a processing aid.
  • compositions contain stabilizing amounts of tetrakis [methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane (0.05 weight percent) and distearylthiodipropionate (0.2 weight percent) as antioxidants, 2(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole (0.5 weight percent) as a UV stabilizer and calcium stearate (0.05 weight percent) as a processing aid.
  • tetrakis [methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane 0.05 weight percent
  • distearylthiodipropionate 0.2 weight percent
  • 2(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole 0.5 weight percent
  • calcium stearate 0.05 weight percent
  • one presently preferred polypropylene composition consists essentially of 66 to 89 weight percent polypropylene, 10 to 33 weight percent of a polyamide dye receptor, 0.25 to 2 weight percent of a carboxylic acid metal salt, specifically sodium benzoate, and the balance being conventional antioxidants, a UV stabilizer and a processing aid.
  • Another presently preferred polypropylene composition containing a different dye receptor consists essentially of 90 to 93 weight percent polypropylene, 6 to 8 weight percent of ethylene/N,N-dimethylaminoethyl methacrylate copolymer, and 0.25 to 1 weight percent of a carboxylic acid metal salt, specifically sodium benzoate, with the balance being conventional antioxidants, a UV stabilizer and a processing aid.

Abstract

Improved dyeability of alpha-monoolefin polymers is obtained by incorporating in the olefin polymer a polymeric dye receptor and a small amount of a carboxylic acid metal salt.

Description

This application is a continuation of application Ser. No. 366,108, filed Apr. 6, 1982, now abandoned; which was a continuation of Ser. No. 171,920, filed July 24, 1980, now abandoned; which was a continuation of Ser. No. 596,486, filed July 16, 1975, now abandoned; which was a continuation of Ser. No. 427,209, filed Dec. 21, 1973, now abandoned; which was a continuation-in-part of Ser. No. 273,619 filed July 20, 1972, now abandoned; which was a continuation-in-part of Ser. No. 207,637, filed Dec. 13, 1971, now abandoned.
This invention relates to dyeable polymer alloy fibers.
In one of its more specific aspects, this invention relates to dyeable olefinic polymers and, in particular, to polypropylene.
The difficulty of dyeing olefin polymers is well known. Considerable attention has been directed to the solution of this problem as reflected by such patents as U.S. Pat. Nos. 3,107,228, 3,312,755 and 3,361,843.
In general, these patents product a dyeable composition by blending with the olefin polymer, dye receptors such as those delineated in the above patents. These include polyamides which are polycondensates of cyclic amides, and polyamides which are polycondensates of aliphatic diamines with dicarboxylic acids, polyurethanes, polyureas, polyesters which are polycondensates of alkylene glycols with dicarboxylic acids, reaction products of polyalkyleneimines containing 2 to 20 carbon atoms with a substance selected from the group consisting of chlorinated paraffin waxes, diisocyanates, lower aliphatic acid anhydrides, hydrohalogen acids and monobasic fatty acid chlorides.
Such dye receptors include mixtures of a polyalkyleneimine in which the alkylene group contains from 2 to 20 carbon atoms with the reaction product of epoxy resin obtained by reacting epichlorohydrin and 4,4'-dioxyphenyldimethyl-methane and monoethanolamine. Such dye receptors also include thermoplastic polymers of vinyl-substituted mono- and polycyclic pyridine bases, thermoplastic polyamides, including condensation homopolymers and copolymers having pendent groups, containing or consisting of amide groups, and amine polymers, including condensation homopolymers and copolymers, in which the amine group is an integral part of the polymer chain, and addition homopolymers and copolymers having pendent groups which include or consist of amine groups and other basic nitrogen polymers such as polyurethanes, polyureas, poly(vinyl carbazoles) and aniline-formaldehyde resins.
It has now been discovered that the extent to which such alphamonoolefin polymers are made dyeable by the inclusion of such dye receptors as those maintained is unexpectedly extended if there is included in the blend of the alloy, that is, in the blend of the olefinic polymer and the dye receptor, a metal carboxylate, that is, a carboxylic acid metal salt such as potassium benzoate, lithium benzoate and sodium benzoate.
As mentioned, this invention is applicable to any of the olefin polymers but is particularly applicable to polypropylene. In general, any dye receptor which when blended with an alpha-monoolefin improves the dye receptivity of the alpha-monoolefin, can be used in this invention.
The olefin polymer will have blended with it any of the aforementioned polymers such as polyamides, polyurethanes and the like as recited in U.S. Pat. Nos. 3,107,228, 3,312,755 and 3,361,843, which substances are referred to hereinafter generally as "dye receptors". The blend of the olefin polymer and the dye receptor will be comprised of up to about 50 weight percent of the dye receptor, an amount in the range of from 1 to about 40 weight percent being preferably employed, the olefin polymer and the dye receptor containing stabilizers, antioxidants and other constituents in conventional amounts.
Preferred dye receptors are polyamides such as nylon-6,6, nylon-6,10, nylon-6, du Pont's Zytel 63, a polymer consisting of nylon-6,6, nylon-6,10 and nylon-6 in a ratio of about 40:40:20, and du Pont's Acid Dye Additive PB 7007, a copolymer of ethylene and an amino alkyl acrylate, specifically a 70/30 ethylene/N,N-dimethylaminoethyl methacrylate copolymer.
Any metal salt of carboxylic acid metal salt which contains 4 to 18 carbon atoms can be used. Suitable carboxylic acids are benzoic acid, p-t-butylbenzoic acid, phenylacetic acid, mellitic acid, 1,8-naphthalic acid, o-phthalic acid, 1,2-cyclohexanedicarboxylic acid, adipic acid, succinic acid, and camphoric acid, stearic acid, and the like. Preferred metals are those of Group IA and Group IIIA of the Periodic Table. It is preferred that the metal salt be finely divided for best results. For example, it is desirable that the salt can pass through a 100 mesh screen or finer, i.e., 325 mesh screen.
Examples of suitable metal salts include sodium benzoate, potassium benzoate, lithium benzoate, sodium stearate, potassium adipate, lithium phenylacetate, aluminum hydroxy p-t-butylbenzoate, and the like. The carboxylic acid metal salt will be employed in an amount up to about 3 weight percent based upon the polyolefin content of the polymeric blend although amounts within the range of from about 0.25 to 1 weight percent are preferred.
The blend of the olefin polymer, the dye receptor and the carboxylic acid metal salt can be prepared in any manner resulting in a homogeneous mixture. Preferably, the olefin polymer and dye receptor are melt blended and the salt is mixed into the blend. Preferred blends contain from about 89.5 to 97 weight percent polypropylene, about 3 to about 10 weight percent of Dye Additive PB 7007, and about 0.25 to 1 weight percent sodium benzoate.
Olefin polymers, and especially polypropylene, require protection against thermal and oxidative degradation and hindered phenolic antioxidants such as Irganox 858, 1010, 1076, and 1093 are excellent for this purpose. These materials are manufactured by the Geigy Chemical Corporation, as disclosed in U.S. Pat. No. 3,285,855, and are, respectively, 2,4-bis(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octylthio)-1,3,5-triazine, tetrakis [methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, octadecyl[3-(3,5-di-t-butyl-4-hydroxyphenyl)]propionate and di-n-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate. These antioxidants are particularly effective because of their low volatility and long term beneficial effects. Other hindered phenols such as BHT(2,6-di-t-butyl-4-methylphenol), Ethyl 330 (Ethyl Corp.), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene can also be used. These primary antioxidants are generally used in amounts ranging from about 0.005 to about 1 weight percent, based on total composition, and more preferably from about 0.02 to about 0.5 weight percent.
A second antioxidant to supplement or augment the effectiveness of the primary one is generally used in polypropylene formulations. A particularly effective class of such compounds are the diesters of beta,beta'-dithiopropionic acid. Especially preferred for this purpose are dilaurylthiodipropionate (DLTDP) and distearylthiodipropionate (DSTDP). These compounds are used in amounts ranging from about 0.02 to about 3 weight percent, based on total composition, and more preferably from 0.05 to about 1.5 weight percent.
A processing aid is generally used in preparing fibers from polypropylene compositions. This material is an alkaline earth metal stearate, preferably calcium stearate. These compounds are used in amounts ranging from about0.005 to about 2 weight percent, based on total composition, and more preferably from about 0.02 to about 0.5 weight percent.
A UV stabilizer is required to impart light stability and dye lightfastness to the compositions. The hydroxybenzotriazoles are effective when used for this purpose. These compounds are represented by the following generic formula: ##STR1## in which R1 and R2 can be hydrogen or an alkyl group containing from 1 to 12 carbon atoms with at least one R1 or R2 being an alkyl group and R3 is a halogen such as chlorine or hydrogen. Particularly preferred is the combination wherein R1 and R2 are C5 and R3 is hydrogen. This compound is 2(2'-hydroxy-3',5'-di-t-amylphenyl)benzotrizole (Tinuvin 328). The UV stabilizer is used in amounts ranging from about 0.1 to about 2 weight percent, based on total composition, and more preferably from about 0.25 to 1.5 weight percent.
A presently preferred composition consists of:
______________________________________                                    
Polypropylene       91.7   weight percent                                 
Polymer dye receptor (du Pont                                             
                    7.0    weight percent                                 
PB 7007)                                                                  
Sodium benzoate     0.5    weight percent                                 
UV stabilizer (Tinuvin 328)                                               
                    0.5    weight percent                                 
Antioxidant (DSTDP) 0.2    weight percent                                 
Antioxidant (Irganox 1010)                                                
                    0.05   weight percent                                 
Calcium stearate    0.05   weight percent                                 
______________________________________                                    
When any of the usually employed dye receptors are blended with an olefin polymer, there is formed an alloy which possesses a dyeability greater than that possessed by the olefin polymer in respect to disperse and acid dyes but substantially no greater than that possessed by the olefin polymer in respect to cationic dyes.
When sodium benzoate is introduced into the blend of the dye receptor and olefin polymer, there is formed a polymeric composition which possesses a dyeability greater than that possessed by the composite of the olefin and the dye receptor in respect to acid dyes but substantially no greater than that of the composite in respect to cationic dyes, and disperse dyes.
The invention is exemplified by the following examples which are not intended to limit the invention.
EXAMPLE I
Blends of polypropylene and Zytel 63, a polyamide manufactured by du Pont, were prepared by melt blending, the blends differing in respect to their polyamide content. To individual portions of these blends, sodium benzoate was added.
All samples were dyed in the same bath with 3 percent owf of Merpacyl Blue SW anionic dye (C.I. 62105), at a pH of 3.5 and a bath liquor ratio of 70:1.
K/S color determinations were made, these employing a colorant-mixture computer devised by Davidson and Hemmendinger, an analogy instrument employing the Kubelka-Munk K/S function. The results are presented below with the higher K/S color values indicating the greater dyeability.
              TABLE I                                                     
______________________________________                                    
Polypropylene,                                                            
          Dye Receptor,                                                   
                       Sodium Benzoate,                                   
                                    K/S                                   
Wt. %     Wt. %        Wt. %        Color                                 
______________________________________                                    
100        0           0            --                                    
80        20           0            2.57                                  
79        20           1            13.7                                  
84        15           1            8.12                                  
89        10           1            4.26                                  
______________________________________                                    
These data indicate the magnitude of the improvement upon addition of sodium benzoate. It will be seen that the addition of 1% sodium benzoate to the blend more than compensated for the removal of 10 weight percent of the dye receptor from the blend.
EXAMPLE II
Blends of polypropylene and Rhodiaceta DD Nylon 66, a polyamide dye receptor, were prepared by melt blending, the blends differing in respect to their polyamide content. To individual portions of these blends sodium benzoate was added.
All samples were dyed in the same bath with 3% owf Merpacyl Blue SW (Color Index Number 62105) at a pH of 3.5. Results were as follows:
              TABLE II                                                    
______________________________________                                    
Polypropylene,                                                            
          Dye Receptor,                                                   
                       Sodium Benzoate,                                   
                                    K/S                                   
Wt. %     Wt. %        Wt. %        Color                                 
______________________________________                                    
66        33           1.0          12.72                                 
73        26           1.0          8.07                                  
79        20           1.0          3.81                                  
86        13           1.0          2.10                                  
90         9           1.0          1.35                                  
94         5           1.0          0.60                                  
78        20           2.0          4.00                                  
______________________________________                                    
The above data indicate the effectiveness of the sodium benzoate in comparatively small quantities and that at one weight percent sodium benzoate concentrations in the composition, the presence of the dye receptor becomes particularly effective at concentrations above about 20 weight percent.
EXAMPLE III
Blends of polypropylene and a polymer comprising a 70/30 ethylene/N,N-dimethylaminoethyl methacrylate copolymer as the dye receptor were prepared, the blends containing 7 percent of the dye receptor. The blends of these polymers were printed, as fibers, with various dyes using 1 percent dye in a dye paste.
To like samples of the same blends, 1 weight percent sodium benzoate was added and the blends of these polymers were printed as fibers, under substantially identical conditions. Results were as follows:
______________________________________                                    
                 Sodium Benzoate in                                       
                 Fiber, Weight Percent:                                   
K/S Values Upon Printing*                                                 
                   0         1                                            
______________________________________                                    
With Isolan Red 2G.sup.(1)                                                
                   10.2      15.4                                         
With Isolan Yellow NW.sup.(1)                                             
                   11.2      20.8                                         
With Merpacyl Blue 2GA.sup.(2)                                            
                   11.6      15.6                                         
______________________________________                                    
 *Color Index Numbers                                                     
 .sup.(1) No number listed, neutral premetallized dyes by Verona Dyestuffs
 Div. of VeronaPharma Chemical Corp., Union, N.J.                         
 .sup.(2) 62125.                                                          
These data indicate that the inclusion of the benzoic acid metal salt is effective with a variety of dyes.
The compositions of this invention are particularly employable as melt-spun fibers because of the depth of dye penetration effected by the components of the composition. As such they are particularly suitable for fabrics subjected to frequent dry cleaning because of the dry cleaning fastness of these fibers.
It has also been found that the dyeability of olefin polymer fibers containing a polymer dye receptor and a carboxylic acid metal salt of the nature defined are not appreciably affected by heat and ultraviolet exposure as compared to similarly treated olefin polymer fibers containing the polymer dye receptor but not containing the carboxylic acid metal salt. The fiber of this invention, when given a heat stabilization step, will not be adversely affected by the subsequent thermal treatment normally required during processing of the fiber.
For convenience, heat stabilization of the fibers of the examples was accomplished by steaming in an autoclave. Commercially, the heat stabilization can be by heat setting such that the dyeable fiber will be maintained at a higher temperature for a much longer period than is usually the case in fiber line drawing.
These improved characteristics of the fibers of this invention are shown by the following:
EXAMPLE IV
Fiber 12 was a polypropylene fiber containing the aforementioned 7% by weight of du Pont's Acid Dye Additive PB 7007 and 1% by weight of sodium benzoate.
Fiber 6 was the same polypropylene fiber containing 7% by weight of du Pont's Acid Dye Additive PB 7007.
Under substantially identical conditions, the fibers were exposed for 20 standard fading hours to a carbon arc and were then dyed, in pairs, in competitive dyeing with an unexposed sample of the same composition, the resulting dye uptake being as follows:
______________________________________                                    
            K/S Value                                                     
Fiber         Untreated Treated                                           
______________________________________                                    
12            17.9      12.2                                              
 6            18.8       5.7                                              
______________________________________                                    
The above data indicate that not only did Fiber 12 undergo a smaller change in dyeability but its dyeability after treatment was considerably greater than that of the non-invention fiber.
The fibers, as described, were heated in an autoclave at 212° F. for an identical period of time. The fibers were then dyed in competitive dyeing, in pairs, with the following results:
______________________________________                                    
            K/S Value                                                     
Fiber         Untreated Treated                                           
______________________________________                                    
12            16.3      18.2                                              
 6            19.0      11.6                                              
______________________________________                                    
Again, the superiority of the fiber of this invention is indicated.
Under substantially identical conditions, the fibers were heated in an autoclave at 212° F. to heat-stabilize them and then exposed for 20 standard fading hours to a carbon arc and thereafter competitively dyed. Results were as follows:
______________________________________                                    
            K/S Value                                                     
Fiber         Untreated Treated                                           
______________________________________                                    
12            14.8      14.7                                              
 6            17.9       4.3                                              
______________________________________                                    
The superiority of the fiber of this invention is again indicated.
It will be evident from the foregoing that various modifications can be made to the method of this invention. Such, however, are considered to be within the scope of the invention.
The compositions in the preceding examples all contained additives not specifically named. In Examples I and II, the compositions contain stabilizing amounts of dilaurylthiodipropionate (0.25 weight percent based on the polypropylene) and 2,4-bis(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octylthio)-1,3,5-triazine (0.08 weight percent based on the polypropylene) as antioxidants and 0.05 weight percent calcium stearate (based on the polypropylene) as a processing aid. In Examples III and IV, the compositions contain stabilizing amounts of tetrakis [methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane (0.05 weight percent) and distearylthiodipropionate (0.2 weight percent) as antioxidants, 2(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole (0.5 weight percent) as a UV stabilizer and calcium stearate (0.05 weight percent) as a processing aid.
Based upon the preceding examples, one presently preferred polypropylene composition consists essentially of 66 to 89 weight percent polypropylene, 10 to 33 weight percent of a polyamide dye receptor, 0.25 to 2 weight percent of a carboxylic acid metal salt, specifically sodium benzoate, and the balance being conventional antioxidants, a UV stabilizer and a processing aid. Another presently preferred polypropylene composition containing a different dye receptor consists essentially of 90 to 93 weight percent polypropylene, 6 to 8 weight percent of ethylene/N,N-dimethylaminoethyl methacrylate copolymer, and 0.25 to 1 weight percent of a carboxylic acid metal salt, specifically sodium benzoate, with the balance being conventional antioxidants, a UV stabilizer and a processing aid.

Claims (32)

I claim:
1. A composition of matter which comprises:
(a) an alpha-monoolefin polymer;
(b) a polymeric dye receptor which when incorporated in a composition comprising said alphamonoolefin polymer improves the acid dyeability of said composition; and
(c) a Group IA metal salt of a carboxylic acid selected from the group consisting of benzoic acid, p-t-butylbenzoic acid, phenylacetic acid mellitic acid, 1,8-naphthalic acid, and o-phthalic acid.
2. A composition of matter in accordance with claim 1 wherein said Group IA metal salt comprises sodium benzoate.
3. A composition of matter in accordance with claim 2 wherein said alpha-monoolefin polymer is polypropylene.
4. A composition of matter in accordance with claim 3 wherein said polymeric dye receptor comprises a copolymer of ethylene and N,N-dimethylaminoethyl methacrylate.
5. A composition of matter in accordance with claim 3 wherein said polymeric dye receptor comprises a copolymer of ethylene and an amino alkyl acrylate.
6. A composition of matter in accordance with claim 1 wherein said polymeric dye receptor comprises a copolymer of ethylene and N,N-dimethylaminoethyl methacrylate.
7. A composition of matter in accordance with claim 1 wherein said polymeric dye receptor comprises a copolymer of ethylene and an amino alkyl acrylate.
8. A composition of matter in accordance with claim 1 wherein said polymeric dye receptor is selected from the group consisting of polyamides which are polycondensates of cyclic amides; polyamides which are polycondensates of aliphatic diamines with dicarboxylic acids; polyurethanes; polyureas; polyesters which are polycondensates of alkylene glycols with dicarboxylic acids; reaction products of polyalkyleneimines containing 2 to 20 carbon atoms with a substance selected from the group consisting of chlorinated paraffin waxes, diisocyanates, lower aliphatic acid anhydrides, hydrohalogen acids and monobasic fatty acid chlorides; and thermoplastic polymers of vinyl-substituted mono- and polycyclic pyridine bases.
9. A composition of matter in accordance with claim 8 wherein said polymeric dye receptor is present in a dye-enhancing amount up to about 50 weight percent of said composition of matter and said Group IA metal salt is present in a dye-enhancing amount up to about 3 weight percent of said composition of matter.
10. A composition of matter in accordance with claim 9 wherein said Group IA metal salt comprises sodium benzoate.
11. A composition of matter in accordance with claim 10 wherein said alpha-monoolefin polymer is polypropylene.
12. A composition of matter in accordance with claim 11 wherein said polymeric dye receptor is a polyamide.
13. A composition of matter in accordance with claim 12 wherein said polypropylene is present in an amount within the range of about 66 to about 89 weight percent of said composition of matter, said polyamide is present in an amount within the range of about 10 to about 33 weight percent of said composition of matter, and said sodium benzoate is present in an amount of up to about 3 weight percent of said composition of matter.
14. A composition of matter in accordance with claim 13 wherein said polyamide comprises nylon-6,6, nylon-6,10 and nylon-6 in a weight ratio of about 40:40:20.
15. A composition of matter in accordance with claim 13 wherein said polyamide comprises nylon-6,6.
16. A composition of matter in accordance with claim 12 consisting essentially of 66 to 89 weight percent polypropylene, 10 to 33 weight percent polyamide, 0.25 to 2 weight percent sodium benzoate, 0.005 to about 1 weight percent of a hindered phenolic antioxidant, 0.02 to about 3 weight percent of a diester of beta,beta'-dithiopropionic acid, 0.005 to about 2 weight percent of an alkaline earth metal stearate processing aid, and 0.01 to about 2 weight percent of a hydroxybenzotriazole as a UV stabilizer.
17. A composition of matter in accordance with claim 16 wherein said hindered phenolic antioxidant is tetrakis [methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, wherein said diester is distearylthiodipropionate present in an amount in the range of 0.05 to about 1.5 weight percent, wherein said alkaline earth metal stearate processing aid is calcium stearate present in an amount in the range of 0.02 to about 0.5 weight percent, and wherein said hydroxybenzotriazole is 2(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole present in an amount in the range of 0.25 to 1.5 weight percent.
18. An article formed of a composition of matter in accordance with claim 1 which has been heat stabilized.
19. An article formed of a composition of matter in accordance with claim 1 which has been heated to at least about 212° F. to stabilize the dyeability of the article.
20. A composition of matter which comprises:
(a) an alpha-monoolefin polymer;
(b) a dye-enhancing amount up to 50 weight percent of an ethylene/N,N-dimethyl-aminoethyl methacrylate copolymer dye receptor;
(c) a dye-enhancing amount up to 3 weight percent of a Group IA metal salt of carboxylic acid selected from the group consisting of benzoic acid, p-t-butylbenzoic acid, phenylacetic acid, mellitic acid, 1,8-naphthalic acid, and o-phthalic acid.
21. A composition of matter in accordance with claim 20 wherein said alpha-monoolefin polymer is polypropylene.
22. A composition of matter in accordance with claim 21 wherein said metal salt is sodium benzoate.
23. A composition of matter in accordance with claim 22 wherein said polypropylene is present in an amount in the range of about 89.5 to about 97 weight percent of said composition, said copolymer is present in an amount within the range of about 3 to about 10 weight percent of said composition, and said sodium benzoate is present in an amount within the range of about 0.25 to about 1 weight percent of said composition.
24. A composition of matter in accordance with claim 22 wherein said polypropylene is present in an amount of about 92 weight percent of said composition, said copolymer is present in an amount of about 7 weight percent of said composition, and said sodium benzoate is present in an amount of about 1 weight percent of said composition.
25. A composition of matter in accordance with claim 22 consisting essentially of 90 to 93 weight percent polypropylene, 6 to 8 weight percent of said copolymer, 0.25 to 1 weight percent of sodium benzoate, 0.005 to about 1 weight percent of a hindered phenolic antioxidant, 0.02 to about 3 weight percent of a diester of beta,beta'-dithiopropionic acid, 0.005 to about 2 weight percent of an alkaline earth metal stearate processing aid, and 0.1 to about 2 weight percent of a hydroxybenzotriazole as a UV stabilizer.
26. A composition of matter in accordance with claim 25 wherein said hindered phenolic antioxidant is tetrakis [methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, wherein said diester is distearylthiodipropionate, said diester being present in the range of 0.05 to about 1.5 weight percent, wherein said alkaline earth metal stearate processing aid is calcium stearate, said calcium stearate being present in the range of 0.02 to about 0.5 weight percent, and wherein said hydroxybenzotriazole is 2(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole which is present in the range of 0.25 to 1.5 weight percent.
27. A composition of matter in accordance with claim 20 wherein said metal salt is sodium benzoate.
28. A composition of matter in accordance with claim 20 in which said composition is heat stabilized.
29. Polypropylene compositions consisting essentially of (a) polypropylene; (b) copolymer consisting essentially of ethylene and an amino alkyl acrylate compound, the content of said copolymer being 1 to 40 weight percent based upon the weight of the blend of said polypropylene and said copolymer; and (c) sodium benzoate, the content of sodium benzoate being 0.25 to 3 weight percent based on polypropylene.
30. Polyolefin compositions according to claim 29 wherein said aminoalkyl acrylate compound is N,N-dimethylaminoethyl methacrylate.
31. A composition of matter in accordance with claim 1 wherein said polymeric dye receptor is a resinous polymeric dye receptor.
32. A composition of matter in accordance with claim 1 wherein said polymeric dye receptor is a polymer having pendent groups containing or consisting of amide groups.
US06/562,029 1971-12-13 1983-12-15 Dyeable polymer alloy fibers containing a polymeric dye-receptor and a metal salt of a carboxylic acid Expired - Fee Related US4490494A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US06/562,029 US4490494A (en) 1971-12-13 1983-12-15 Dyeable polymer alloy fibers containing a polymeric dye-receptor and a metal salt of a carboxylic acid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20763771A 1971-12-13 1971-12-13
US06/562,029 US4490494A (en) 1971-12-13 1983-12-15 Dyeable polymer alloy fibers containing a polymeric dye-receptor and a metal salt of a carboxylic acid

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US06366108 Continuation 1982-04-06

Publications (1)

Publication Number Publication Date
US4490494A true US4490494A (en) 1984-12-25

Family

ID=26902423

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/562,029 Expired - Fee Related US4490494A (en) 1971-12-13 1983-12-15 Dyeable polymer alloy fibers containing a polymeric dye-receptor and a metal salt of a carboxylic acid

Country Status (1)

Country Link
US (1) US4490494A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4582877A (en) * 1984-07-27 1986-04-15 The Dow Chemical Company Transamidated poly-2-oxazoline compositions useful as wetting agents for polymer and absorbents for polar materials
US5985999A (en) * 1993-07-13 1999-11-16 Huntsman, Petrochemical Corporation Dyeable polyolefin containing polyetheramine modified functionalized polyolefin
US6093496A (en) * 1998-05-12 2000-07-25 Huntsman Petrochemical Corporation Polyolefin containing polyetheramine modified functionalized polyolefin
US6146574A (en) * 1993-07-13 2000-11-14 Huntsman Petrochemical Corporation Article manufacture using polyolefin containing polyetheramine modified functionalized polyolefin

Citations (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2770518A (en) * 1952-10-20 1956-11-13 Celanese Corp Dyed textile materials and method of making
US2984634A (en) * 1957-01-30 1961-05-16 Eastman Kodak Co Crystalline polymerized monoolefinic hydrocarbons containing metal salt of carboxylic acid
CA627346A (en) * 1961-09-12 Osterloh Fritz Carrier substance in dyestuffs for the dyeing of plastic masses
FR1320986A (en) * 1962-03-02 1963-03-15 Ici Ltd Process for the production of colored articles composed of poly-alpha-olefins
FR1327339A (en) * 1961-05-15 1963-05-17 Eastman Kodak Co Easy-to-dye manufactured items based on crystallizable hydrocarbon polymers
FR1330784A (en) * 1961-05-15 1963-06-28 Eastman Kodak Co Articles manufactured from crystalline polymers
GB932897A (en) * 1961-01-19 1963-07-31 Du Pont Polypropylene compositions
CA690402A (en) * 1964-07-07 Behrenbruch Horst Process for the manufacture of improved shaped articles of linear polyolefins
US3153106A (en) * 1961-10-11 1964-10-13 Glanzstoff Ag Production of novel effect fabrics and filaments and yarns therefor
CA709302A (en) * 1965-05-11 Asahi Kasei Kogyo Kabushiki Kaisha Process for dyeing polyolefin articles
US3207739A (en) * 1962-04-26 1965-09-21 Shell Oil Co Polymer crystallization method
US3207736A (en) * 1960-12-21 1965-09-21 Shell Oil Co Polymer crystallization
GB1007753A (en) * 1961-05-15 1965-10-22 Eastman Kodak Co Olefinic hydrocarbon polymer compositions
US3215486A (en) * 1962-04-17 1965-11-02 Toyo Spinning Co Ltd Fixation of polypropylene fibers impregnated with dyestuffs and other treating agents
US3240552A (en) * 1961-05-15 1966-03-15 Eastman Kodak Co Crystalline polymerized alpha-monoolefinic hydrocarbons containing an organic addition polymer and a metal compound to improve their dyeability
US3245751A (en) * 1962-05-24 1966-04-12 Montedison Spa Textile fibers having improved dyeability and method of preparing same
GB1029447A (en) * 1964-02-21 1966-05-11 Sumitomo Chemical Co Polyolefin composition
US3268499A (en) * 1965-09-10 1966-08-23 Shell Oil Co Polymer crystallization method
US3312755A (en) * 1956-12-12 1967-04-04 Montedison Spa Readily dyeable compositions consisting of isotactic polypropylene and from 0.1 to 200deg. of a member selected from the group consisting of polyamides, polyurethanes, polyesters and polyalkyleneimine reaction products
GB1066460A (en) * 1963-09-30 1967-04-26 Toyo Rayon Co Ltd Improvements in or relating to polyolefinic compositions containing metal compounds
GB1078585A (en) * 1965-05-14 1967-08-09 Montedison Spa Improving olefin polymer dye receptivity
GB1082584A (en) * 1965-02-17 1967-09-06 Asahi Chemical Ind Dyeable poly-ª‡-olefinic compositions
US3361843A (en) * 1964-06-15 1968-01-02 Uniroyal Inc Method of dyeing a blend of a polyolefin and a nitrogen containing polymer by using a dyebath containing lewis acids
US3367926A (en) * 1964-03-25 1968-02-06 Dow Chemical Co Modification of crystalline structure of crystallizable high polymers
GB1104059A (en) * 1966-02-11 1968-02-21 Montedison Spa Receptivity of polymers to dyestuffs
US3382305A (en) * 1954-10-29 1968-05-07 Du Pont Process for preparing oriented microfibers
US3413249A (en) * 1964-06-22 1968-11-26 Shell Oil Company Of New York Coloring of polystyrene
US3433853A (en) * 1966-05-25 1969-03-18 Hercules Inc Polyolefin compositions containing a basic polyamide dye site additive
US3439999A (en) * 1964-09-28 1969-04-22 Uniroyal Inc Cross-dyed carpets
GB1157500A (en) * 1966-03-07 1969-07-09 Montedison Spa Dyeing of Olefin Polymers.
US3482926A (en) * 1961-04-24 1969-12-09 Montedison Spa Halogenating fibers composed of mixtures of polypropylene and a basic nitrogen containing polymer
GB1178506A (en) * 1967-05-22 1970-01-21 Phillips Petroleum Co Dyeable Polyolefins.
US3502422A (en) * 1966-02-17 1970-03-24 Uniroyal Inc Dye-bath treatment for polymeric articles
GB1197277A (en) * 1968-06-08 1970-07-01 Vickers Zimmer Ag Dyeable polypropylene compositions
CA849612A (en) * 1970-08-18 Uniroyal Ltd. - Uniroyal Ltee. Dyeable polyolefin composition
US3551401A (en) * 1966-06-18 1970-12-29 Asahi Chemical Ind Easily dyeable polyolefin composition
US3555805A (en) * 1965-09-14 1971-01-19 Ici Ltd Filaments of a synthetic organic polymer
US3772411A (en) * 1971-04-19 1973-11-13 Shell Oil Co Alkali metal salts of aralkanoic or aralkenoic acids to improve dyeability of polyolefin compositions

Patent Citations (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA690402A (en) * 1964-07-07 Behrenbruch Horst Process for the manufacture of improved shaped articles of linear polyolefins
CA849612A (en) * 1970-08-18 Uniroyal Ltd. - Uniroyal Ltee. Dyeable polyolefin composition
CA627346A (en) * 1961-09-12 Osterloh Fritz Carrier substance in dyestuffs for the dyeing of plastic masses
CA709302A (en) * 1965-05-11 Asahi Kasei Kogyo Kabushiki Kaisha Process for dyeing polyolefin articles
US2770518A (en) * 1952-10-20 1956-11-13 Celanese Corp Dyed textile materials and method of making
US3382305A (en) * 1954-10-29 1968-05-07 Du Pont Process for preparing oriented microfibers
US3312755A (en) * 1956-12-12 1967-04-04 Montedison Spa Readily dyeable compositions consisting of isotactic polypropylene and from 0.1 to 200deg. of a member selected from the group consisting of polyamides, polyurethanes, polyesters and polyalkyleneimine reaction products
US2984634A (en) * 1957-01-30 1961-05-16 Eastman Kodak Co Crystalline polymerized monoolefinic hydrocarbons containing metal salt of carboxylic acid
US3207736A (en) * 1960-12-21 1965-09-21 Shell Oil Co Polymer crystallization
GB932897A (en) * 1961-01-19 1963-07-31 Du Pont Polypropylene compositions
US3482926A (en) * 1961-04-24 1969-12-09 Montedison Spa Halogenating fibers composed of mixtures of polypropylene and a basic nitrogen containing polymer
FR1330784A (en) * 1961-05-15 1963-06-28 Eastman Kodak Co Articles manufactured from crystalline polymers
GB1007753A (en) * 1961-05-15 1965-10-22 Eastman Kodak Co Olefinic hydrocarbon polymer compositions
US3240552A (en) * 1961-05-15 1966-03-15 Eastman Kodak Co Crystalline polymerized alpha-monoolefinic hydrocarbons containing an organic addition polymer and a metal compound to improve their dyeability
FR1327339A (en) * 1961-05-15 1963-05-17 Eastman Kodak Co Easy-to-dye manufactured items based on crystallizable hydrocarbon polymers
US3153106A (en) * 1961-10-11 1964-10-13 Glanzstoff Ag Production of novel effect fabrics and filaments and yarns therefor
FR1320986A (en) * 1962-03-02 1963-03-15 Ici Ltd Process for the production of colored articles composed of poly-alpha-olefins
US3215486A (en) * 1962-04-17 1965-11-02 Toyo Spinning Co Ltd Fixation of polypropylene fibers impregnated with dyestuffs and other treating agents
US3207739A (en) * 1962-04-26 1965-09-21 Shell Oil Co Polymer crystallization method
US3245751A (en) * 1962-05-24 1966-04-12 Montedison Spa Textile fibers having improved dyeability and method of preparing same
GB1066460A (en) * 1963-09-30 1967-04-26 Toyo Rayon Co Ltd Improvements in or relating to polyolefinic compositions containing metal compounds
GB1029447A (en) * 1964-02-21 1966-05-11 Sumitomo Chemical Co Polyolefin composition
US3395198A (en) * 1964-02-21 1968-07-30 Sumitomo Chemical Co Polyolefin composition containing ethylene-aminoalkyl acrylate copolymer
US3367926A (en) * 1964-03-25 1968-02-06 Dow Chemical Co Modification of crystalline structure of crystallizable high polymers
US3361843A (en) * 1964-06-15 1968-01-02 Uniroyal Inc Method of dyeing a blend of a polyolefin and a nitrogen containing polymer by using a dyebath containing lewis acids
US3413249A (en) * 1964-06-22 1968-11-26 Shell Oil Company Of New York Coloring of polystyrene
US3439999A (en) * 1964-09-28 1969-04-22 Uniroyal Inc Cross-dyed carpets
GB1082584A (en) * 1965-02-17 1967-09-06 Asahi Chemical Ind Dyeable poly-ª‡-olefinic compositions
GB1078585A (en) * 1965-05-14 1967-08-09 Montedison Spa Improving olefin polymer dye receptivity
US3268499A (en) * 1965-09-10 1966-08-23 Shell Oil Co Polymer crystallization method
US3555805A (en) * 1965-09-14 1971-01-19 Ici Ltd Filaments of a synthetic organic polymer
GB1104059A (en) * 1966-02-11 1968-02-21 Montedison Spa Receptivity of polymers to dyestuffs
US3502422A (en) * 1966-02-17 1970-03-24 Uniroyal Inc Dye-bath treatment for polymeric articles
GB1157500A (en) * 1966-03-07 1969-07-09 Montedison Spa Dyeing of Olefin Polymers.
US3433853A (en) * 1966-05-25 1969-03-18 Hercules Inc Polyolefin compositions containing a basic polyamide dye site additive
US3551401A (en) * 1966-06-18 1970-12-29 Asahi Chemical Ind Easily dyeable polyolefin composition
GB1178506A (en) * 1967-05-22 1970-01-21 Phillips Petroleum Co Dyeable Polyolefins.
GB1197277A (en) * 1968-06-08 1970-07-01 Vickers Zimmer Ag Dyeable polypropylene compositions
US3772411A (en) * 1971-04-19 1973-11-13 Shell Oil Co Alkali metal salts of aralkanoic or aralkenoic acids to improve dyeability of polyolefin compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4582877A (en) * 1984-07-27 1986-04-15 The Dow Chemical Company Transamidated poly-2-oxazoline compositions useful as wetting agents for polymer and absorbents for polar materials
US5985999A (en) * 1993-07-13 1999-11-16 Huntsman, Petrochemical Corporation Dyeable polyolefin containing polyetheramine modified functionalized polyolefin
US6146574A (en) * 1993-07-13 2000-11-14 Huntsman Petrochemical Corporation Article manufacture using polyolefin containing polyetheramine modified functionalized polyolefin
US6093496A (en) * 1998-05-12 2000-07-25 Huntsman Petrochemical Corporation Polyolefin containing polyetheramine modified functionalized polyolefin

Similar Documents

Publication Publication Date Title
US3915930A (en) Flame-retardant composition
CA1085602A (en) Multi-component stabilizing system for pigmented polyolefins
CA1237845A (en) Polyamides containing phenolic compounds
DE1817212A1 (en) Alkyl hydroxyphenyl polyamides
US4490494A (en) Dyeable polymer alloy fibers containing a polymeric dye-receptor and a metal salt of a carboxylic acid
US4746692A (en) Polyolefin compositions for use with water systems
JP3113958B2 (en) Stabilizer mixture
DE2204495A1 (en) Stabilized polyamide compositions
EP0512955B1 (en) Stabilized hot melt adhesive systems
US4377651A (en) Polyolefin stabilization
US4066610A (en) Stabilized pigmented polyolefin compositions
JPH0657644B2 (en) Stabilized antimicrobial agent
KR960015632B1 (en) Polypropylene stabilized against oxidative degradation with mixtures of diarylamine derivatives and sterically hindered phenols
DE3233353A1 (en) STABILIZED SYNTHETIC RESIN
US3928504A (en) Dyeable polypropylene compositions containing a polyamine adduct
DE10134327A1 (en) Sterically-hindered phenol mixing oligomeric butylated reaction product of p-cresol and cyclopentadiene is used as the sole primary antioxidant for polyamides
EP0271235A2 (en) Polypropylene stabilized against oxidative degradation with mixtures of aralkyl-substituted diarylamines and sterically hindered phenols
DE2309435A1 (en) PROCESS FOR STABILIZING POLYAMIDES
US4052351A (en) Stabilization of olefin polymers
US5607989A (en) Piperidinyl phosphite compositions and polyolefin compositions containing them
US4069277A (en) Dyeable polyamides containing an antistatic agent
JPS63161043A (en) Polyolefin stabilized to oxidation breakdown
WO2001046310A1 (en) Mixtures of phosphanes and chromane derivatives
DE69907270T2 (en) LIGHT-STABLE COPOLYETHERESTER COMPOSITION
DE2260993C3 (en) Colorable compounds based on polyolefins

Legal Events

Date Code Title Description
FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19921227

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362